Lubricant containing pour point depressant



.tion residue from the above Patented Apr. 26, 1949 UNITED STATE LUBRICANT CONTAINING POUR POINT DEPBESSANT Eugene Lieber, New Y Cashman, Bayonne,

Westfleld, N.

ork,

N. Y., and Edward P.

and Raymond M. Dean,

J., assignors velopment Company,

to Standard Oil Dea corporation of Delaware No Drawing. Application December 28, 1944, Serial No. 570,206

Claims.

This invention relates to novel condensation products and to methods of preparing and using same and more particularly it relates to the treatment of high molecular weight chemical condensation products having wax modifying properties and having the ability to depress the pour point of waxy mineral lubricating oils when added thereto in small amounts, so as to improve the pour stability characteristics thereof.

Wax modifying agents or pour depressors may be prepared by a number of different methods already known to the art, such as by condensation of relatively long chain paraffinic materials, e. g. chlorinated paraifin wax having a chlorine content of about 10 to 18% chlorine and derived from a paraflin wax having a melting point of 120 to 160 F. or so, or olefins derived therefrom by dehydrochlorination, with aromatic hydrocarbons such as naphthalene, benzene, anthracene and the like, or with other aromatic compounds such as phenol and its homologues. Such condensation is generally effected by means of a Friedel-Crafts catalyst, preferably aluminum chloride, or others such as zinc chlorine, iron chloride, or other halides of these metals, or boron fluoride. The condensation is generally carried out at temperatures ranging from room temperature up to 300 F., preferably not higher than about 170 or 180 F. During the reaction, inert solvents may be used such as refined kerosene or heavy petroleum naphtha, or inert highly chlorinated solvents such as tetrachlorethane, dichlorbenzene, etc. The order of adding the reagents and catalyst may vary. For instance, the chlorinated wax and naphthalene may be mixed together first and then the catalyst added last, or the catalyst may be mixed with the aromatic compound and then the chlorinated wax added last. After the condensation has been completed the residual catalyst is usually hydrolyzed by addition of water, alcohol, caustic soda, or mixtures thereof, and finally the reaction products are subjected to distillation under reduced pressure such as up to 500 or 600 F. under a vacuum at least as low as 20 mm, mercury absolute pressure or with fire and steam distillation.

The condensation product obtained as distillaolescribed process is generally a complex mixture of chemical compounds having an average molecular weight between the approximate limits of 1000 and 2000 or so and ordinarily has good pour depressing potency; for instance, when a small amount thereof such as 1 or 2% or even a much smaller 'amount such as 0.1% is added to a waxy mineral lubricating oil for instance having a relatively high pour point of F., the pour point of the resultant blend will be much lower such as below 0 5'. and may be as low as F. or considerably lower. Even small amounts of pour depressor such as 0.1, or .05% may effect a substantial pour depressing action.

While the wax modifiers made in the above manner have excellent pour depressing properties as measured by the A. S. T. M. (American Society of Testing Materials) procedure, they do not have as good pour tions of winter storage the pour point of a blend of waxy lubricating oil containing such pour depressor may on certain occasions rise to relatively high Values such as to render ineffective the original purpose of the pour depressor. An article by C. E. Hodges and A. B. Boehm published in the Oil and Gas Journal, volume 42, page 103, June 26, 1942, on pour point stability of pour depressant treated oils under winter storage discusses more in detail the problem of pour stability and suitable test for determining the stable pour point temperature of oils. Briefly, the test, often referred to as test V procedure comprises heating the oil containing the pour depressor to F, to insure complete solution of the pour depressor, then subjected to six cycles consisting of cooling the blend to 28' F. and warming up to temperatures ranging from 40 F. in the second cycle, by 10 F. stages, down to 0 F. in the sixth cycle, the samples being tilted every 5 F. during the cooling stages and their temperatures and fluidity recorded. A complete report of the test includes a statement of the solid (the highest temperature at which the point sample was solid) in each cycle, but the essential feature of the test is a report of the stable pour point which is considered to be 5 F. higher than the highest solid point noted in any of the cycles. When subjected to this test, the waxy oils containing the wax modifiers discussed above, generally show stable pour points ranging from --15 F. to as high as +15 F. or so depending upon the type and amount of pour depressor used, in spite of the fact that these same blends show regular A. S. T. M. pour points generally much lower.

It has now been discovered, and is the chief feature of the present invention, that the pour stability characteristics of such wax modifiers can be very greatly improved by subjecting the wax modifiers to a secondary chemical condensation with a low molecular weight polyhalomethane compound. Such reagent should have the general formula R-nCXn where R represents like or unlike radicals consisting of hydrogen or low molecular weight hydrocarbon groups, X is halogen and n is at least 2. At least 1 R is preferably an aromatic hydrocarbon group, and n is preferably 2. Thus preferred examples of this condensation reagent are benzal chloride CcHsCHCh, dichlormethyl naphthalene, or naphthyl dichlormethane CmHqCI-IClz, dichlormethyl xylene (CH3) 2CBH3CHC12 stability properties as de-' sired. More specifically, under certain condi- A reaction mixture.

dlphenyl dichlormethane (CaHalzCClz. and the like, although other compounds coming within the general class mentioned above may be used such as benzal bromide or iodide, benzotrichloride CsHsCCla, dichlorm'ethyl anthracene CuHcCHCla, dichlormethyl diphenyl CzzHcCHClz, methylene dichloride or dichlormethane HaCClz, ethylene dichloride or methyl dichlormethane CHaCHClz, etc. The secondary reaction, 1. e. the condensation of the original wax modifier with the polyhalomethane compound may be brought about under substantially the same conditions as used in the primary reaction and with the same type of catalyst, etc., but it is found that this reaction -proceeds with greater ease than the first condensation, chlorinated solvents, e. g. tetrachlorethane give better results than hydrocarbon solvents, and in general, lower temperatures may be used.

Two alternative procedures may be used in carrying out the present invention. One is, as described-above, to first make and completely isolate the primary condensation product or wax modifier and then subject it to the secondary condensation with polyhalomethane compound directly to the first condensation reaction mixture without hydrolysis and removal of residual catalyst and distillationof the reaction mixture to obtain the first condensation product in a pure and isolated condition. As compared'to the separate two-step process, the direct one-step process has several distinct advantagesnameiy-that it only requires one catalyst hydrolysis step instead of two, and it eliminates extra washing and distillation of the condensation product from, the first condensation.

The final condensation product. of this inven- 1 4 tion of an excess of isopropyl alcohol and aqueous caustic soda and the aluminum hydroxide produced by hydrolysis was removed. The product was then distilled to remove the diluent and the unreacted constituents to a temperature of 600 F. with fire and steam. The material recovered as the distillation residue is a wax modifying agent and is referred to here and after as the initial condensation product of Example 1. 200 grams of this initial condensation product was recovered in 300' cc. of tetrachlor-ethane as solvent. To this is added 15 grams of aluminum chloride and the temperature adjusted to 90 F. 30 grams of benzal chloride are then added to the reaction mixture with agitation over a period of 30 minutes. After the addition of the benzal chloride the reaction temperature was main tained at 90 F. for a period of 2% hours after which it was diluted with a liter of solvent and the aluminum chloride'destroyed by neutralizing with a mixture of alcohol and water. After settling and discarding the aqueous layer the product obtained was distilled with me and steam at 600 F. The yield of. material weighing'l98 gramswas' obtained as product.

The product obtained as described above was tested for ordinary pour depressant potency by the standard A. S. T. M. procedure in two different types of waxy lubricating oils, the following results being obtained;

tion has a substantially higher molecular weight than the wax modifying starting material, and although the mechanism of the chemical reaction involved is not known with certainty, or the reason why this reaction should make a product of such superior pour stability characte istics. it is believed that one molecule of the polyhalomethane compound condenses with two molecules of the aliphatic aromatic wax modifier causing what may be termed an interlinking thereof through their aromatic nuclei. It appears to be essentialor at least very advantageous to have the aromatic portions of the wax modifier starting material brought very close together by being attached to a single aliphatic carbon atom in the polyhalomethane compound. Examination or the product tested by the by ultraviolet light indicates a higher molecular weight in the aromatic portion of the molecule as compared to the wax modifier starting material; The molecular weight of this final product is believed between the approximate limits of 2000 and 5000, and preferably about 3000 to 4000. It is ordinarily an extremely viscous liquid having for instance a viscosity of about 2500 to 10,000 seconds, preferably about 4000 to 5000 seconds, Saybolt at 210 F.

The objects and advantages of the invention will be better understood from the following examples.

' EXAMPLE 1 A pour point depressant is produced by condensing 100 parts by weight of chlorparafiln (14% chlorine) with 15 parts by weight of naphthalene using 2 /2 parts by weight of aluminum chloride as the catalyst, adding the chlorwax last to the The reaction was conducted ata temperature of about 88 of about 30-40 parts (based on chlorparaflin) of kerosene as solvent. After a reaction time of 4 hours the catalyst is hydrolyzed by the addi- F. in the presence Percent Product added to 13 13 F. a F. v None +30 +30 0.03 +5 -5 .5 -15 The pour stability properties of the product were "Test V" procedure, in a United 180 neutral alone, referred to as Oil A which is a parafiinic light lube oil, and the same oil containlug-2% of Panhandle bright stock which blend is referred to as Oil 13. Table I shows in detail the solid points obtained in the individual cycles and Table -II summarizes'the results.

Table J Solid loints in Cycle 2 a s c OllA-i-l .d.A .Q -12 -19 -s -s -'i Oil A 1% onzal cond. prod. oi 1 o-it 'i i'fiii'li "'18 "it *2 13 it 1 on a 1 isms! cqnd. prod. oi

Ex.1 -l6 22 18 -20 -23 1 Indicates that the samgle did not go solid. Oil B is oil A right stock.

- Table Ii Hi hest Stable git? tar r a a":

o [1 cs on Number v (OF) (0F) Oil A 1 p. d. A all 5 8 3 Oil A i Benzal cond a. a 2 *2 3 Oil B 1 7}, Banzai cond prod. of ELI None None None -28 I Still fluid in all cycles. I Oil B is oil A 2% bright stock. 1 As indicated in Table 11, whereas the stable a 'very viscous dark brown pour point of the commercial pour depressor A was minus 3, that of the condensation product of Example 1 was minus 10 F., which is a very substantial improvement. In fact, the original wax stantial improvement. From a practical point of view, columns 1 and 2 show even more strikingly the superiority of the benzal condensation prod uct of this invention, by showing that in 1% conmodifier used as starting material in Example centration the blend containing this addition 1 is a material of the same general type as the agent only became solid once in all of the cycles, commercial pour depressor A, and therefore, it whereas pour depressor A became solid 4 times. is clear that the secondary reaction of this in- It is interesting to note in column 5 for comvention namely, the condensation product of the parison that the A. S. T. M. pour points of the war: modifier with benzal chloride, was respontwo blends containing 1% of addition agent were sible for the reduction of the stable pour point of at least as low as minus 25 F., whereas the best the commercial pour depressor A from minus 3 stable pour point was minus 16; in fact, the down to minus 10 F. This is important not only A. S. T. M. pour points for the blends containing due to the actually lower stable pour point, but 1% of pour depressor A, and the benzal condenalso because during various cycles of alternating sation product, were inversely proportional to mild and cold temperature conditions during the the stable pour points. It is obvious, therefore, winter months, the oil containing pour depressor that the stable pour point and the number of A may become solid many times more than the times which a sample becomes solid in the 5 cy-' same oil containing the benzal-treated pour decles of the stable pour point test, are better cri- Pr er; in the "Test V" 9011 st l ty test. as in- 20 teria of the practical merits of a pour depressor. Qdicated in Tables I and II both oils A and B con- ,-taining pou'r' depressor A became solid five times, EXAMPLE 3 whereas similar blends containing the benzaltreated product only became solid two times for The following Proportion 0f reagents w t 11 A blend, and none for t 1 B m r used: 2 gals. dichlor benzene as solvent, 15 lbs., EXAMME 2 3 oz. naphthalene, 16 gals. chlorinated wax (14.6% C1), 3 lbs., 2 oz. AlCls, in carrying out the Another series of tests was made in order to reaction the reactor was charged with the sol; impare the 9 Stability Characteristics of the vent, naphthalene and aluminum chloride. The same two additives Example 1 (except chlorinated wax was then added to the reaction that fufierent sample OI l depressor A was mixture while agitating over a period of minused) m dmerent lubricating on base stock utes. The reaction temperature was raised from namely, a blend (identified as oil C) of paraf- Q a finic lubricating oil or medium viscosity, referred zgg gfg zg ggfigfi g 2 to as Baton Rouge 442 neutral, containing 5% 35 d t d t 22,, F e g i t t s of Panhandle bright stock. Table III shows in t e 0 an ma n aued area for detail the solid points obtained in the individual f 4 At this M the cycles of the pour stability test, and T m W tion 13 lbs 6 oz. of benzal chloride were added summarizes the results, the A. S. T. M. pour point a penofl of 35'minutesh was also being shown for comparison. 1m extremely vigorous and a considerabl "amount Tabl in of foaming took place such that an additional 2 gals. of solvent was added during the course of solid Points in Cycle the benzal Chloride. th-Q addition of the benzal chloride the reaction mixture was 2 a 4 s s maintained at 125 F. for an additional 30 minutes whereupon the temperature was reduced to on c+o.5% p. on; 2 +14 +10 +2 6 about 100 F. and the aluminum chloride de- 88I6% 353 +2 I stroyed with a mixture of 6 gals. of aqueous so- 3 5 dium hydroxide (25%) and 8 gals. isopropyl al- 33.55153Z1Zi3iiffiif; -2-i -2o -20 -20 -21 cohol. The product was recovered as described 11 d t th ttbe Sam is did not osolid y in Example 2' I p l ifi gfe i sa aple than sed in Exa mple 1. 6 p stability Properties were tested y Table IV Solidin Highest Stable A. s. "r. M. Additive Clygle gag is olg it a Pon m:

8% lrifigigiii::::::::::::::::::::::: "1 2,4322% 13 3 Oil C+0.5% cnzal cond. prod. of Ex. l. 3, 4, 5, 6 4 +6 11 l5 Oil C+1.0% Benzal cond. prod. of Ex. 1 6 1 -21 l6 a -25 Difierent sample than used in Example 1. Here again n Table IV, a in Table 1 0f Test -V" procedure and the following results ample 1, the benzal condensation product showed were obtained; substantially superior pour stability characteristies as compared to the commercial pour de- Test. Solid Pm pressor A. This is not only seen in column 4 fg ge t showing that the stable pour point with the w W Cycle, benzal condensation product was minus 16 F. 11g 1% concentration, whereas pour depressor A ha m m M $8 r d 0.4 -2 +1 stable pour points of only 7 F. The extra ret 00 5 p 0 c 1 ,12 fig 33 duction in stable pour point from plus 7 to minus Benmlwn pmdummx'z 1.0 8 -s i8 is very difficult to obtain and is a very subto recovering the invention can be obtained by carrying out. the

benzal condensation immediately after eflecting the primary condensation and before actually primary condensation product from the reaction mixture, thereby avoiding duplication of the recovery steps including hydrolysis and removal of residual lation under reduced pressure to remove solvent and any volatile condensation products.

EXAMPLE 4 A wax modifier was made according to the paragraph), and then 100 parts by weight 01' this initial. condensation product were dissolved in 200 parts by weight of dichlorbenzene solvent, after which 7.5 parts by weight of aluminum chloride were added, and finally parts by weight of benzal chloride were added with stirring, the reaction temperature being about 90 F. After a reaction period of about hour, the re-' action was stopped and the final? condensation product was recovered in the same manner as described" in the, second paragraph pie 1. The initial condensation product and the benzal condensation product were then examined for pour stability characteristics while subjecting them to the Test V" procedure through the third cycle, the results of the second andthlrd cycles being'shown in the follow= ing table:

under. Exam catalyst and distil I Table V Pmem Test V Solid Pt.

addlthe I Cycle 2. Cycla 3 Init. cond. prod. Ex. 4 1.0 2 +4 Benzal cond. prod. Ex. 4 I 1.0 l&

The above results show that the final benzal,

condensation eifected a very substantial improve-' ment in the pour stability characteristics, namely by lowering the solid point of the second cycle from -2 to 16, and in the third 'cyclefrom +4 to 12-, when the condensation products were used in -l.0 concentration.

V EXAMPLE 5 I Another wax modifier was made according to the general procedure described in Example 1 (1st paragraph), and the resulting initial condensation was 'further condensed with benzal chloride using the procedure described above under Example 4, except that the final condensation reaction was permitted to go for a longer time, samples being 1 hours, the flnal condensation product being in each case recovered and tested for pour stability characteristics as in Example 4 with the following results:

Table VI Test V Solid Pt. Per cent additive Cycle 2 Cycle 3 Init. cond. prod. Ex. 5.. at; 2 Benza] cond. prod. Ex. 5 after 1 hr.

reaction 2 3 Benn-ii cond. prod. Ex. 5 after 1% hr. reaction 5g i 6 except that taken after about 1 hour and condensation, when wax (14.5%

8 The above results indicate that the benzal time of 1 hour or 1 hours, gave, in both instances, a very substantial improvement in both stability characteristic Another test was made to show the application of the invention with only one catalyst removal step and one final distillation step; in other words the general procedure used was the same as that described in Example 3.

12.0 parts by weight of naphthalene and 11.3 partsv by weight of dichlorbenzene as solvent were charged into a reactor, then 2.3 parts by weight of aluminum chloride catalyst were added, and finally parts by weight of chlorinated chlorine content). A reaction temperature of about F. was maintained for 4 hours and then 5.2 parts by weight of benzal chloride were added with continued stirring the benzal condensation reaction was carried out for one hour and then residual catalyst was destroyed and removed and the dual condensation product was recovered by fire and steam distillation up to 570 as follows, showing for comparison the initial condensation products of,Ex amp'le 1.-

Table I!!! P Cent Test V Solid Pt.

Ad e es 2 Cycle 3 Init. cond. prod. of Ex. 1 0. 4 2 +12 Banzai cond.prod. of Ex. 6 0.4 -10 5 1 Test oil is +15% bright stock.

The above data show that the benzal condensation effects a very substantial improvement in pour stability when applied without intermediate isolation of the initial" condensation product.

- Examrnrs, 7 AND 8 Two additional tests were made using the same general procedure as outlined in Example much larger quantities of materials were usedand two diflerept proportions of benzal chloride were used. In Example 8 the amount of benzal chloride used was the same as Example 6, whereas in Example 7 only 70% as much benzal chloride was. used. After 4 hours the benzal chloride was added, using 390 pounds in Example 7 and 520 pounds in Example 8, with stirring, and the reaction was permitted to continue for an additional'4 hours, samples being withdrawn at various intervals to charge the progress of the I mine the optimum reaction period. A benzal condensation reaction period of about 2 hours gave the best results, although fairly good results were obtained within the broader range of about 1 to 3 hours.

When tested in 1% concentration in a wax mineral lubricating oil blend of oil A to which had been added 2.5% of Panhandle bright stock, the following pour stability tests were obtained in cycles 2 and 3, showing for the sake of comparison an initial tion product similar to, but not identical with. those referred to in previous examples.

carried out with a reaction F. Pour stability tests were condensation and to deterwax-naphthalene condensa- Table VII! Test V Solid Pt. in-

Cycle 2 Cycle 3 5 Benzsl cond. prod. Ex. 7 g Bcrizel cond. prod. Ex. 8 7 lnit. oond. prod 2 +2 The above data show that the benzal condensation efieoted a very substantial improvement in pour stability in both Examples 7 and 8.

Exacsetn 9 The following table presents the A. S. T. M.

Pour Depressant data:

Percent Product added to egg fifg The pour stability properties or the product were tested by the Test-V procedure in a paraffin light lube oil containing 3.5% Panhandle bright stock. Tablelx shows in detail the solid points in the individual cycles incomparison with Pour Depressant A referred to in Example 1.

Table IX Solid Points in Per cent Cycle 2 Cycle 3 Oil 1.25 p. d. A +18 +12 0il+l.50p.d.. i. +2 4 Oil 1.25 (CsFi'shCCh cond. prod 21 -12 Oil 1.50 (GiEmCCl 00nd. prod -18 -l4 1 Indicates that the sample did not go solid.

As indicated in Table IX, the stable pour points of commercial pour depressant A were lowered from 10 to 40 R, which is a substantial improvement.

EXAMPLE} 10 In this test the same general procedure was followed as in Example 6, except that 12 parts of diphenyl dichloro methane were added instead of the benzal chloride. 67 parts of solvent and 4 parts of catalyst were also added with the modifier. Pour stability tests were as follows, showing for comparison the initial condensation product of Example 1. v

Table X Test V Solid Points Per cant I ddi tive 1 Cycle 2 Cycle 3 Inltialcond.prcd.oiEx.1 1;? f; 1: 00nd. prod. of Ex. 10 tag 1 Note: Test oil is a light psraflinic lube oil 3.5 percent Pan-- handle bright stock.

! Indicates that the sample did not go solid.

The above data show that the condensation effectsa. very substantial improvement in pour stability when applied without intermediate isolation of the initial condensation product.

EXAMPLE 11 Commercial pour depressant B, reported to be a wax-phenolic condensation product, was modifled by benzal chloride using a similar procedure as used in Example 1. In this case grams of the initial wax-modifying agent were used instead of 200 grams. Other proportions of reactants and procedure were the same.

The pour stability properties of the product were tested by the Test V procedure, Table XI showing the solid points obtained in the individual cycles in comparison with the solid points of the commercial pour depressant B.

Table Xi Test V Solid Points Per Cent Additive Cycle 2 Cycle 3 I Commercial Pour Depressant B if :g :15

Commercial Pour Depressant B condensed 1. 25 -20 4 Commercial Pour Depressant B with benzal chloride 1. 5 -23 -7 1 Indicates sample did not go solid. galore: Test oil-light paraiiinic-lube oi1+3.5% Panhandle bright As indicated in Table XI a substantial improvement in pour stability was obtained by condensation of the reported wax-phenol commercial pour depressant with benzal chloride.

It is not intended that this invention be limited to the specific examples which have been given merely for the sake of illustration nor necessarily by any theory as to the mechanism of the operation of the invention, but only by the appended claims in which it is intended to claim all novelty inherent in the invention as well as all modifications coming within the scope and spirit of the invention.

We claim:

1. The process of improving the pour point stability of a wax modifier made by an initial Friedel-Crafts condensation of about 1 to 5 mols of chlorinated paraffin wax containing about 10 to 20% of chlorine with one moi of a low molec ular weight aromatic compound in the presence of an inert solvent, to make an initial condensation product having a molecular'weight of at least 1,000 and having wax modifying properties, comprising subjecting said initial condensation product to a further Friedel-Crafts condensation with an aryl polyhalomethane compound, hydrolyzing and removing the catalyst and distilling the reaction products under reduced pressure to at least 500 F. to obtain the desired condensation product as distillation residue.

- naphthalene.

8. Process according to claim 1v in which the low. molecular weight aromatic compound used is phenol.

4. Process according to claim 1 in which the polyhalomethane compound is benzal chloride.

5. In the process of making a wax modifier by condensation of about 100 parts by weight of chlorinated paraflln wax containing about 14% chlorine with about 15 parts by weight of naphthalene in the presence or aluminum chloride as catalyst and in the presence of a refined kerosene as a solvent, to make an initial condensation product having a molecular weight of at least 1,000 and having pour depressing properties, the improvement comprising subjecting said initial condensation product to a further condensation with about 30 parts by weight of benzal chloride in the presence of aluminum chloride as catalyst and in the presence of an initial solvent, hydrolyzing and removing the catalyst, and subjecting the reaction products to fire and steam distillation up to 600 F. to obtain as distillation residue a final condensation product or improved pour stability characteristics. f

0. Process according to claim in which the initial condensation product is recovered from the initial condensation reaction products by hydrolysis and removal of catalyst and distilla-' tlon under reduced pressure before subjecting it to the final condensation step.

7. Process according to claim 5 in which the primary condensation product is subjected to the final condensation reaction without recovering it from the primary reaction products.

8. A product comprising essentially a product obtained by the Friedel-Crafits condensation of 15 to 30 parts by weight of an aryl substituted polyhalomethane compound and 100 to 200 parts by weight of a Friedel-Crafts condensation product of a chlorinated paraffin wax having a chlorine content of to 18% by weight and a compound selected from the class consisting of naphthalene and phenol at a temperature in the range of from room temperature to about 300 F., said product being hydrolyzed, the catalyst removed and the product distilled under reduced pressure to at least 500 F. obtaining the desired condensation product as a distillation residue.

9. A lubricant having an improved stable pour mint comprising essentially a product obtained by the Friedel-Crafts condensation of 15 to parts by weight of an aryl substituted polyhalomethane compound and .100 to 200 parts by weight of a Friedel-Crafts condensation product of a chlorinated paraflln wax having a chlorine content of- 10 to 18% by weight and a compound selected from the class consisting of naphthalene and phenol at a temperature in the range of room temperature to about 300 F., said product being hydrolyzed, the catalyst removed and distilledv ing a chlorine content of 10 to 18% by weight and a compound selected from the class consisting of naphthalene and phenol at a temperature in the range of room temperature to about 300 F., said initial condensation product having a molecular weight ranging from 1,000 to 5,000, said benzal chloride wax aromatic product being hydrolyzed, catalyst removed and product distilled under reduced pressure to at least 500 F. to obtain the desired product as a distillation residue. EUGENE LIEBER.

EDWARD P. CASHMAN. RAYMOND M. DEAN.

REFERENCES CITED 7 The following references are of record in the file of this patent:

UNITED STATES PATENTS.

Number Name Date 1,963,917 McLaren June 19, 1934 2,052,003 Reifl Aug. 25, 1936 2,138,775 Towne NOV. 29, 1938 2,174,246 Lieber Sept. 26, 1939 2,288,319 Mikeska June 30, 1942 2,384,107 Lieber Sept. 4, 1945 2,510,885 Lieber Nov. 12, 1946 OTHER. REFERENCES Anhydrous Aluminum Chloride in Organic Chemistry, by C. A. Thomas, Reinhold Pub. 00., New York, 1941, pages 126 and 127. 

